Classifications

• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
  • C03C10/0036—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
  • C03C10/0009—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing silica as main constituent
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C3/00—Glass compositions
  • C03C3/04—Glass compositions containing silica
  • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
  • C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
  • A61C13/00—Dental prostheses; Making same
  • A61C13/08—Artificial teeth; Making same
  • A61C13/082—Cosmetic aspects, e.g. inlays; Determination of the colour
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
  • A61C13/00—Dental prostheses; Making same
  • A61C13/08—Artificial teeth; Making same
  • A61C13/083—Porcelain or ceramic teeth
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K6/00—Preparations for dentistry
  • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
  • A61K6/802—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics
  • A61K6/822—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics comprising rare earth metal oxides
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K6/00—Preparations for dentistry
  • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
  • A61K6/831—Preparations for artificial teeth, for filling teeth or for capping teeth comprising non-metallic elements or compounds thereof, e.g. carbon
  • A61K6/833—Glass-ceramic composites
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K6/00—Preparations for dentistry
  • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
  • A61K6/831—Preparations for artificial teeth, for filling teeth or for capping teeth comprising non-metallic elements or compounds thereof, e.g. carbon
  • A61K6/836—Glass
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
  • C03B1/00—Preparing the batches
  • C03B1/02—Compacting the glass batches, e.g. pelletising
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
  • C03B11/00—Pressing molten glass or performed glass reheated to equivalent low viscosity without blowing
  • C03B11/12—Cooling, heating, or insulating the plunger, the mould, or the glass-pressing machine; cooling or heating of the glass in the mould
  • C03B11/122—Heating
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
  • C03C10/0036—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents
  • C03C10/0045—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents containing SiO2, Al2O3 and MgO as main constituents
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
  • C03C10/0054—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing PbO, SnO2, B2O3
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C3/00—Glass compositions
  • C03C3/04—Glass compositions containing silica
  • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C3/00—Glass compositions
  • C03C3/04—Glass compositions containing silica
  • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
  • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
  • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C3/00—Glass compositions
  • C03C3/04—Glass compositions containing silica
  • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
  • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
  • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
  • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C4/00—Compositions for glass with special properties
  • C03C4/0007—Compositions for glass with special properties for biologically-compatible glass
  • C03C4/0021—Compositions for glass with special properties for biologically-compatible glass for dental use
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C4/00—Compositions for glass with special properties
  • C03C4/12—Compositions for glass with special properties for luminescent glass; for fluorescent glass
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2201/00—Glass compositions
  • C03C2201/06—Doped silica-based glasses
  • C03C2201/30—Doped silica-based glasses containing metals
  • C03C2201/34—Doped silica-based glasses containing metals containing rare earth metals
  • C03C2201/36—Doped silica-based glasses containing metals containing rare earth metals containing rare earth metals and aluminium, e.g. Er-Al co-doped
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2205/00—Compositions applicable for the manufacture of vitreous enamels or glazes
  • C03C2205/06—Compositions applicable for the manufacture of vitreous enamels or glazes for dental use

Definitions

• the present invention relates to glass-ceramics and glasses which contain europium and are particularly suitable for the production of dental restorations whose fluorescent properties largely correspond to those of natural teeth.
• the invention also relates to a method for producing the glass ceramics and glasses according to the invention and their use as dental material and in particular for producing dental restorations.
• Glass ceramics are used in dentistry because of their good mechanical and optical properties, especially for the production of dental crowns and small bridges.
• EP 0 877 071 A1 describes glasses and glass ceramics that contain, among other things, Eu 2+ ions and exhibit long-lasting phosphorescence.
• DE 10 2009 013 377 A1 describes the use of a borosilicate glass doped with CeO 2 or at least one oxide of another lanthanoid, including Eu 2 O 3 , to increase the counterfeit security of a packaging by emitting electromagnetic radiation in the range between 300 and 700 nm when exposed to UV -Light.
• WO 2015/173230 A1 describes a method for producing a lithium silicate glass or a lithium silicate glass ceramic, in which a melt of a starting glass containing cerium ions is exposed to reducing conditions. As a result, Ce 4+ ions contained in the starting glass are to be wholly or partially reduced to Ce 3+ ions which, due to 5d ⁇ 4f transitions, show fluorescence in the wavelength range from 320 to 500 nm.
• a corresponding method for producing a glass ceramic with SiO 2 as the main crystal phase or a glass that contains nuclei for the crystallization of SiO 2 is over WO 2017/080853 A1 known.
• the glasses and glass ceramics known from the prior art have inadequate fluorescence properties and, in particular under UV light, cannot sufficiently imitate the fluorescence properties of the natural tooth material.
• the known materials do not show the required fluorescence at all relevant wavelengths in the UV range.
• dental restorations made from such glass ceramics are recognizable as restorations, in particular under the influence of UV light, or are perceived as tooth gaps or defects.
• heat treatments under oxidizing conditions, for example during sintering result in a considerable impairment of the fluorescence properties of the glasses and glass ceramics produced in this way.
• the invention is based on the object of providing glass ceramics and glasses which show fluorescence at excitation wavelengths in the entire relevant UV range, especially in the range from 250 nm to 430 nm and in particular in the range from 360 nm to 430 nm, and are therefore particularly suitable for It is suitable to manufacture dental restorations that not only have good mechanical properties, but also can largely imitate the fluorescence properties of natural tooth material at excitation wavelengths in the entire relevant UV range.
• the glass-ceramics and glasses should also be suitable as mixing components for adjusting the fluorescence properties of other glasses and glass-ceramics.
• a glass or a glass ceramic containing europium which contains the following components: SiO 2 30.0 to 75.0 Al 2 O 3 10.0 to 45.0 Europium calculated as Eu 2 O 3 0.05 to 5.0.
• the glass according to the invention and the glass ceramic according to the invention show improved fluorescence properties compared to the prior art at excitation wavelengths in the range from 250 to 430 nm and in particular also at excitation wavelengths in the range from 360 to 430 nm and that these fluorescence properties are also largely stable Heat treatments and oxidizing conditions are.
• the glass and the glass ceramic contain 32.0 to 72.0, in particular 35.0 to 65.0 and preferably 38.0 to 50.0% by weight of SiO 2 .
• the glass and the glass ceramic 15.0 to 40.0, in particular 20.0 to 40.0, preferably 25.0 to 40.0 and particularly preferably 30.0 to 40.0 wt .-% Al 2 O 3 included.
• the glass and the glass ceramic preferably contain 0.1 to 4.0, in particular 0.3 to 3.0, preferably 0.5 to 2.0, more preferably 0.6 to 1.0 and particularly preferably 0.65 to 0 , 85 wt% europium, calculated as Eu 2 O 3 .
• the glass and the glass ceramic have 8.0 to 30.0% by weight, in particular 12.0 to 29.0, preferably 15.0 to 28.0 and particularly preferably 20.0 to 27.0 %
• Me II O Me II O being selected from MgO, CaO, SrO and / or ZnO.
• the glass and the glass ceramic contain 8.0 to 30.0, in particular 12.0 to 29.0, preferably 15.0 to 28.0 and particularly preferably 20.0 to 27.0% by weight of CaO and / or SrO.
• Glasses and glass ceramics which contain at least one and preferably all of the following components in the specified amounts are particularly preferred: component Wt% MgO 0 to 13.0, especially 3.5 to 13.0 CaO 0 to 22.0, especially 5.0 to 22.0 SrO 0 to 28.0, especially 9.0 to 28.0 ZnO 0 to 5.0, especially 4.0 to 5.0.
• the glass and the glass ceramic contain 0 to 10.0, in particular 0 to 5.0 and preferably 0 to 1.0% by weight of BaO and most preferably are essentially free of BaO.
• the glass and the glass ceramic contain 0 to 2.0, in particular 0.1 to 1.2 and preferably 0.3 to 0.7% by weight of tin, calculated as SnO.
• the glass and the glass ceramic also preferably contain 0 to 5.0, preferably 0.5 to 4.0 and preferably 1.0 to 3.0% by weight of cerium, calculated as CeO 2 .
• the glass and the glass ceramic can furthermore contain alkali metal oxide MeI 2 O in an amount of 0 to 15.0, in particular 0 to 10.0, preferably 0 to 5.0, particularly preferably 0 to 1.0 and most preferably 0 to 0 , 5% by weight, this Me I 2 O being selected in particular from Li 2 O, Na 2 O, K 2 O, Rb 2 O and Cs 2 O and preferably being selected from Li 2 O, Na 2 O and K 2 O.
• MeI 2 O alkali metal oxide
• the glass and the glass ceramic at least one and in particular all of the following alkali metal oxides Me I 2 O in the specified amounts: component Wt% Li 2 O 0 to 5.0 Na 2 O 0 to 10.0 K 2 O 0 to 14.0 Rb 2 O 0 to 7.0 Cs 2 O 0 to 13.0.
• the glass and the glass ceramic can also contain 0 to 10.0, in particular 0 to 4.0 and preferably 0 to 2.5% by weight of further oxide of trivalent elements Me III 2 O 3 .
• the term "further oxide of trivalent elements Me III 2 O 3" denotes trivalent oxides with the exception of B 2 O 3 , Al 2 O 3 , Eu 2 O 3 and Ce 2 O 3 , this Me III 2 O 3 being selected in particular from Y 2 O 3 , La 2 O 3 , Ga 2 O 3 and / or In 2 O 3 .
• the glass and the glass ceramic particularly preferably contain at least one and in particular all of the following further oxides of trivalent elements Me III 2 O 3 in the specified amounts: component Wt% Y 2 O 3 0 to 3.0 La 2 O 3 0 to 2.0 Ga 2 O 3 0 to 2.0 In 2 O 3 0 to 1.0.
• the glass and the glass ceramic contain 0 to 3.0, in particular 0 to 2.0 and preferably 0 to 1.0% by weight of B 2 O 3 and most preferably essentially free of B 2 O 3 are.
• the glass and the glass ceramic can contain further oxide of tetravalent elements Me IV O 2 in an amount from 0 to 15.0, in particular from 0 to 4.0 and particularly preferably from 0 to 2.5% by weight.
• the term "further oxide of tetravalent elements Me IV O 2" denotes tetravalent oxides with the exception of SiO 2 , SnO 2 , CeO 2 and TiO 2 , this Me IV O 2 being selected in particular from ZrO 2 and / or GeO 2 .
• the glass and the glass ceramic particularly preferably contain at least one and in particular all of the following further oxides of tetravalent elements Me IV O 2 in the specified amounts: component Wt% ZrO 2 0 to 15.0 GeO 2 0 to 5.0.
• the glass and the glass ceramic contain 0 to 5.0, in particular 0 to 2.5 and preferably 0 to 1.0% by weight TiO 2 and most preferably be substantially free of TiO 2 .
• the glass and the glass ceramic can contain oxide of pentavalent elements Me V 2 O 5 in an amount from 0 to 6.0 and in particular from 0 to 5.0% by weight, this Me V 2 O 5 being selected in particular from P 2 O 5 , V 2 O 5 , Ta 2 O 5 and / or Nb 2 O 5 .
• the glass and the glass ceramic particularly preferably contain at least one and, in particular, all of the following further oxides of pentavalent elements Me V 2 O 5 in the specified amounts: component Wt% P 2 O 5 0 to 6.0 V 2 O 5 0 to 6.0 Ta 2 O 5 0 to 5.0 Nb 2 O 5 0 to 5.0.
• the glass and the glass ceramic can also contain 0 to 6.0% by weight of oxide of hexavalent elements Me VI O 3 , this Me VI O 3 being selected in particular from WO 3 and / or MoO 3 .
• the glass and the glass ceramic particularly preferably contain at least one and in particular all of the following oxides Me VI O 3 in the specified amounts: component Wt% WHERE 3 0 to 6, 0 MoO 3 0 to 5.0.
• the glass and the glass-ceramic can also contain oxides of other f-elements, e.g. Oxides of Pr, Nd, Gd, Tb, Dy, Er and Yb and in particular oxides of Tb and / or Dy.
• Oxides of Pr, Nd, Gd, Tb, Dy, Er and Yb e.g. Oxides of Pr, Nd, Gd, Tb, Dy, Er and Yb and in particular oxides of Tb and / or Dy.
• the glass and the glass ceramic can contain 0 to 5.0 and in particular 0 to 1.0% by weight of fluorine.
• a glass and a glass ceramic which contain at least one and preferably all of the following components in the specified amounts are particularly preferred: component Wt% SiO 2 32.0 to 72.0 Al 2 O 3 15.0 to 40.0 Europium calculated as Eu 2 O 3 0.1 to 4.0 Cerium calculated as CeO 2 0 to 5.0 Tin calculated as SnO 0 to 2.0 Me I 2 O 0 to 15.0 Me II O 0 to 30, 0 Me III 2 O 3 0 to 10.0 Me IV O 2 0 to 15.0 Me V 2 O 5 0 to 6.0 Me VI O 3 0 to 6.0 fluorine 0 to 5.0, where Me I 2 O, Me II O, Me III 2 O 3 , Me IV O 2 , Me V 2 O 5 and Me VI O 3 have in particular the meanings given above.
• the glass and the glass ceramic contain at least one and preferably all of the following components in the specified amounts: component Wt% SiO 2 32.0 to 72.0 Al 2 O 3 15.0 to 40.0 Europium calculated as Eu 2 O 3 0.1 to 4.0 Cerium calculated as CeO 2 0 to 5.0 Tin calculated as SnO 0 to 2.0 Li 2 O 0 to 5.0 Na 2 O 0 to 10.0 K 2 O 0 to 14.0 Rb 2 O 0 to 7.0 Cs 2 O 0 to 13.0 MgO 0 to 13.0 CaO 0 to 22.0 SrO 0 to 28.0 ZnO 0 to 5.0 BaO 0 to 10.0 B 2 O 3 0 to 3.0 Y 2 O 3 0 to 3.0 La 2 O 3 0 to 2.0 Ga 2 O 3 0 to 2.0 In 2 O 3 0 to 1.0 ZrO 2 0 to 15.0 GeO 2 0 to 5.0 TiO 2 0 to 5.0 P 2 O 5 0 to 6.0 V 2 O 5 0 to 6.0
• the glass ceramic according to the invention preferably contains at least one aluminosilicate as the crystal phase and in particular as the main crystal phase.
• the glass ceramic according to the invention contains a calcium aluminosilicate or strontium aluminosilicate or a mixture of these, preferably a calcium aluminosilicate or strontium aluminosilicate, as the crystal phase and in particular as the main crystal phase.
• main crystal phase denotes the crystal phase which has the highest mass fraction of all the crystal phases present in the glass ceramic.
• the masses of the crystal phases are determined in particular using the Rietveld method.
• a suitable method for quantitative analysis of the crystal phases using the Rietveld method is, for example, in Dissertation by M. Dittmer "Glasses and glass ceramics in the MgO-Al2O3-SiO2 system with ZrO2 as nucleating agent", University of Jena 2011 described.
• the glass ceramic according to the invention contains at least 5% by weight, in particular at least 10% by weight and preferably at least 20% by weight aluminosilicate as the crystal phase, in particular in the form of calcium aluminosilicate, strontium aluminosilicate or mixtures of these.
• the type and the amount of crystal phases formed can be controlled in particular by the composition of the underlying glass and the heat treatment that is used to produce the glass ceramic from the glass.
• the examples illustrate this by means of the variation in the composition and the heat treatment used.
• the invention also relates to precursors with a corresponding composition from which the glass ceramic according to the invention can be produced by heat treatment.
• These preliminary stages are a correspondingly composed glass (also referred to as starting glass) and a correspondingly composed glass with germs.
• corresponding composition means that these precursors contain the same components in the same amounts as the glass-ceramic, the components, with the exception of fluorine, being calculated as oxides, as is customary for glasses and glass-ceramics.
• the invention also relates to a glass according to the invention which contains nuclei for the crystallization of an aluminosilicate and in particular of calcium aluminosilicate and / or strontium aluminosilicate.
• Heat treatment of the glass according to the invention can initially produce the glass according to the invention with nuclei, which in turn can be converted into the glass-ceramic according to the invention, in particular with an aluminosilicate as the crystal phase and preferably as the main crystal phase, by further heat treatment.
• the glass according to the invention is produced in particular in such a way that a mixture of suitable starting materials, such as e.g. Carbonates, oxides, phosphates and fluorides, melted at temperatures of in particular 1500 to 1800 ° C for 0.5 to 10 h and the glass melt obtained is added to water to produce granules. After grinding, these granules can then be pressed into a blank, a so-called powder compact, or processed into a powder.
• suitable starting materials such as e.g. Carbonates, oxides, phosphates and fluorides
• the invention is therefore also directed to a method for producing the glass ceramic according to the invention, in which the glass, in particular the glass with nuclei, at least one heat treatment at a temperature of 1000 to 1500 ° C, preferably 1050 to 1450 ° C, for a duration of particularly 10 to 720 minutes and preferably 30 to 120 minutes.
• nucleation can be carried out before the heat treatment in step (b).
• the melt of the starting glass can be reacted with at least one reducing agent.
• all agents which are capable of reducing Eu 3+ ions to Eu 2+ ions under the conditions of the method can be used as reducing agents.
• Those reducing agents are preferred which can be removed from the glass melt without residue after the reduction.
• gaseous reducing agents and reducing agents which are burned out of the glass melt after the reduction under the conditions of the method according to the invention are preferred.
• gaseous reducing agents are gases containing hydrogen and preferably mixtures of hydrogen and nitrogen.
• reducing agents are also substances which contain at least one oxidizable carbon atom, in particular carbon, for example graphite, organic salts, carbohydrates and cereal flours.
• the melt of the starting glass is formed from a glass-forming composition which contains at least one reducing agent.
• a compound is preferred which contains at least one oxidizable carbon atom and is preferably selected from the group consisting of organic salts, carbohydrates and cereal flours. Examples of particularly suitable organic salts are acetates.
• a europium acetate in particular europium (III) acetate hydrate, is used as the reducing agent.
• the at least one reducing agent is a reducing gas, the gas preferably containing hydrogen and preferably containing hydrogen and nitrogen. Mixtures of hydrogen and nitrogen which contain about 5% by volume of hydrogen and are also referred to as forming gas are particularly suitable.
• the extent of the reduction can be controlled via the amount of gas supplied and in particular via the flow rate and duration of the supply of the gas.
• the amount of the active component of the reducing gas, preferably hydrogen is preferably 0.05 to 5 l / min, in particular 0.1 to 1 l / min and preferably 0.2 to 0.5 l / min, for a period of 10 up to 180 minutes, in particular 20 to 120 minutes and preferably 30 to 90 minutes.
• the invention also relates to a glass according to the invention and a glass ceramic according to the invention which have a whitish-blue fluorescent color in the CIE color space.
• the glasses and glass-ceramics according to the invention containing europium are particularly suitable as mixture components for adjusting the fluorescence properties of other glasses and glass-ceramics.
• a glass or a glass ceramic which contains the glass according to the invention or the glass ceramic according to the invention with a content of europium therefore represent a further subject matter of the invention.
• the glass according to the invention or the glass ceramic according to the invention containing europium can in particular be used as a component of an inorganic-inorganic composite or in combination with a large number of other glasses and / or glass ceramics, the composites or combinations in particular being used as dental materials.
• the composites or combinations can particularly preferably be in the form of sintered blanks.
• Examples of other glasses and glass ceramics for the production of inorganic-inorganic composites and combinations are in DE 43 14 817 A1 , DE 44 23 793 Cl, DE 44 23 794 C1 , DE 44 28 839 A1 , DE 196 47 739 A1 , DE 197 25 552 A1 , DE 100 31 431 A1 , EP 0 827 941 A1 , EP 0 916 625 A1 , WO 00/34196 A2 , EP 1 505 041 A1 , EP 1 688 398 A1 , EP 2 287 122 A1 , EP 2 377 831 A1 , EP 2 407 439 A1 , WO 2013/053863 A2 , WO 2013/053864 A2 , WO 2013/053865 A2 , WO 2013/053866 A2 , WO 2013/053867 A2 , WO 2013/053868 A2 , WO 2013/164256 A1 , WO 2014/170168 A
• glasses and glass ceramics belong to the silicate, borate, phosphate or aluminosilicate group.
• Preferred glasses and glass ceramics are of the SiO 2 -Al 2 O 3 -K 2 O type (with cubic or tetragonal leucite crystals), SiO 2 -B 2 O 3 -Na 2 O type, alkali-silicate type, alkali -Zinc-silicate-type, silico-phosphate-type and / or SiO 2 -ZrO 2 -type.
• Lithium silicate glass ceramics are particularly preferred and in particular glass ceramics which have lithium metasilicate or lithium disilicate as the main crystal phase and optionally other crystal phases such as apatite, diopside, Contain quartz and / or wollastonite, and also glass ceramics that contain SiO 2 , in particular in the form of deep quartz, as the main crystal phase.
• glass ceramics which have lithium metasilicate or lithium disilicate as the main crystal phase and optionally other crystal phases such as apatite, diopside, Contain quartz and / or wollastonite, and also glass ceramics that contain SiO 2 , in particular in the form of deep quartz, as the main crystal phase.
• the glass ceramics according to the invention and the glasses according to the invention are in particular in the form of powders, granulates or blanks in any shape and size, e.g. monolithic blanks such as platelets, cuboids or cylinders, or powder compacts, in unsintered, partially sintered or densely sintered form. In these forms they can easily be further processed, e.g. to dental restorations. However, they can also be in the form of dental restorations, such as inlays, onlays, crowns, partial crowns, bridges, veneers, shells or abutments.
• Dental restorations such as inlays, onlays, crowns, partial crowns, bridges, veneers, shells or abutments can be produced from the glass ceramics according to the invention and the glasses according to the invention, in particular in the form of composites and combinations.
• the invention therefore relates to their use as dental material and, in particular, to their use for producing dental restorations. It is preferred here that the glass ceramic or the glass is given the shape of the desired dental restoration by pressing or machining.
• the pressing is usually carried out under increased pressure and temperature. It is preferred that the pressing takes place at a temperature of 700 to 1150 ° C and in particular 700 to 1000 ° C. It is also preferred to carry out the pressing at a pressure of 10 to 30 bar.
• the desired change in shape is achieved through the viscous flow of the material used.
• It can be the inventive Glass and the glass according to the invention with germs and preferably the glass ceramic according to the invention can be used.
• the glasses and glass ceramics according to the invention can be used in particular in the form of blanks of any shape and size, for example solid blanks or powder compacts, for example in unsintered, partially sintered or densely sintered form.
• the machining is usually carried out by material-removing processes and in particular by milling and / or grinding. It is particularly preferred that the machining is carried out as part of a CAD / CAM process.
• the glass according to the invention, the glass with nuclei according to the invention and the glass ceramic according to the invention can be used for machining.
• the glasses and glass ceramics according to the invention can be used in particular in the form of blanks, e.g. Solid blanks or powder compacts, e.g. in unsintered, partially sintered or densely sintered form.
• the glass ceramic according to the invention is preferably used for machining.
• the glass ceramic according to the invention can also be used in a form that is not yet completely crystallized and that has been produced by heat treatment at a lower temperature. This offers the advantage that easier machining and thus the use of simpler apparatus for machining are possible. After such a partially crystallized material has been machined, it is regularly subjected to further heat treatment in order to induce further crystallization.
• the glass ceramics according to the invention and the glasses according to the invention are, however, also suitable as coating material for, for example, ceramics, glass ceramics and metals.
• the invention is therefore likewise directed to the use of the glasses according to the invention or the glass ceramics according to the invention for coating, in particular, ceramics, glass ceramics and metals.
• the invention also relates to a method for coating ceramics, glass ceramics and metals, in which the glass ceramic according to the invention or glass according to the invention, in particular in the form of composites and combinations, is applied to the ceramic, the glass ceramic or the metal and exposed to a temperature of at least 600 ° C becomes.
• glass ceramic according to the invention or glass according to the invention for example in the form of powder compacts or monolithic blanks, at an elevated temperature, for example 700 to 1150 ° C and in particular 700 to 1000 ° C, and using pressure, for example 10 to 30 bar, pressed on.
• the EP 231 773 described method and the press furnace disclosed there are used.
• Suitable commercial ovens are the Programat ovens from Ivoclar Vivadent AG, Liechtenstein.
• the invention therefore also relates to the use of the glass ceramics according to the invention or the glasses according to the invention, in particular in the form of composites and combinations, as dental material and in particular for the production of dental restorations or as a coating material for dental restorations, such as crowns, bridges and abutments.
• the invention therefore also relates to a method for producing a dental restoration, in particular an inlay, onlay, crown, partial crown, bridge, veneer, shell or abutment, in which the Glass ceramic according to the invention or the glass according to the invention, in particular in the form of composites and combinations, is given the shape of the desired dental restoration by pressing, sintering or machining, in particular as part of a CAD / CAM process.
• a total of 21 glasses according to the invention with the compositions specified in Table I were produced, the oxidation states of the specified oxides being based on the oxidation states of the raw materials used.
• the glasses were crystallized into glass ceramics according to Table II.
• the glasses or glass ceramics according to Table III were mixed with other glasses and sintered to form glass ceramic bodies.
• starting glasses with the compositions given in Table I were first melted on a 100 to 200 g scale from customary raw materials at the temperature T S for a duration t S.
• Glass frits were produced by pouring the melted starting glasses into water.
• the fluorescence properties of the glass frits thus obtained at excitation wavelengths of 254, 366, 395 and 430 nm were determined visually using a UV lamp and are shown in Table II. After that, in particular, showed at excitation wavelengths of 366, 395 and 430 nm, all glasses obtained in the examples show fluorescence.
• the glass frits obtained were ground in a zirconium oxide mill to a grain size of ⁇ 45 ⁇ m. Approx. 4 g of these powders were then pressed into cylindrical blanks and sintered according to Table II at a temperature T sinter and a holding time of t sinter to form dense glass-ceramic bodies, this being for sintering temperatures of up to 1200 ° C in a Programat® sintering furnace (Ivoclar Vivadent AG ) in a vacuum and for sintering temperatures above 1200 ° C in a sintering furnace of the type LHT 02/16 (Nabertherm) in a normal atmosphere.
• the fluorescence properties of the glass-ceramics obtained in this way at excitation wavelengths of 254, 366, 395 and 430 nm were determined visually using a UV lamp and are shown in Table II. According to this, the glass ceramics obtained showed fluorescence, in particular at excitation wavelengths of 366, 395 and 430 nm.
• the glass frits obtained in Examples 14 and 21 were comminuted and sieved to a particle size of ⁇ 25 ⁇ m.
• the glass powders obtained were mixed into powdered lithium silicate glasses as shown in Table III. Approx. 4 g of each of these mixtures were then pressed into cylindrical or disk-shaped blanks and sintered in a sintering furnace (Programat® from Ivoclar Vivadent AG) to form dense glass-ceramic bodies.
• the fluorescence properties of the glass-ceramic bodies thus obtained at excitation wavelengths of 254, 366, 395 and 430 nm were visualized determined by means of a UV lamp and are shown in Table III. According to this, all of the glass-ceramic bodies obtained showed fluorescence, particularly at excitation wavelengths of 366, 395 and 430 nm.
• the glass ceramics obtained in Examples 1, 2, 4 and 9 and the glass ceramic obtained in Example 5 after sintering at 1110 ° C. were comminuted and sieved to a grain size of ⁇ 25 ⁇ m.
• the glass ceramic powders obtained were mixed into powdered lithium silicate glasses as shown in Table III. Approx. 4 g of each of these mixtures were then pressed into cylindrical or disk-shaped blanks or press stumps and sintered or hot-pressed in a sintering furnace (Programat® from Ivoclar Vivadent AG) to form dense glass-ceramic bodies.
• the fluorescence properties of the glass-ceramic bodies obtained in this way at excitation wavelengths of 254, 366, 395 and 430 nm were determined visually using a UV lamp and are shown in Table III. According to this, all of the glass-ceramic bodies obtained showed fluorescence, especially at excitation wavelengths of 366 nm.
• Calcium aluminosilicates such as anorthite were obtained as crystal phases in CaO-containing compositions and strontium aluminosilicates such as Slawsonite in SrO-containing compositions.

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• 2019
  • 2019-02-14 EP EP19157306.2A patent/EP3696150A1/fr active Pending
• 2020
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